Polymer compound and organic semiconductor device using the same

Abstract

A polymer compound comprising a structural unit represented by the formula (1): wherein a ring A and a ring B represent a heterocyclic ring. A ring C represents a condensed aromatic heterocyclic ring not having a line-symmetric axis and a rotational axis. Z 1 and Z 2 represent a group represented by the formula (Z-1), a group represented by the formula (Z-2), a group represented by the formula (Z-3), a group represented by the formula (Z-4), a group represented by the formula (Z-5), a group represented by the formula (Z-6) or a group represented by the formula (Z-7). R represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group.].

The invention claimed is: 
     
       1. A polymer compound comprising a structural unit represented by the formula (1): 
       
         
           
           
               
               
           
         
         wherein 
         a ring A and a ring B each independently represent a heterocyclic ring, and the heterocyclic ring optionally has a substituent; 
         a ring C represents a condensed aromatic heterocyclic ring not having a line-symmetric axis and a rotational axis, and the aromatic heterocyclic ring optionally has a substituent; 
         Z 1  and Z 2  each independently represent a group represented by the formula (Z-1), a group represented by the formula (Z-2), a group represented by the formula (Z-3), a group represented by the formula (Z-4), a group represented by the formula (Z-5), a group represented by the formula (Z-6) or a group represented by the formula (Z-7); 
       
       
         
           
           
               
               
           
         
         wherein 
         R represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent; and when a plurality of R are present, they may be the same or different. 
       
     
     
       2. The polymer compound according to  claim 1 , wherein the structural unit represented by the formula (1) is a structural unit represented by the formula (2): 
       
         
           
           
               
               
           
         
         wherein 
         a ring A, a ring B, Z 1  and Z 2  represent the same meaning as described above; 
         X 3  represents an oxygen atom, a sulfur atom or a selenium atom; and 
         a ring D represents an aromatic hydrocarbon ring selected from the group consisting of a benzene ring and a condensed ring obtained by condensation of 2 to 4 benzene rings, and the aromatic hydrocarbon ring optionally has a substituent. 
       
     
     
       3. The polymer compound according to  claim 2 , wherein the structural unit represented by the formula (2) is a structural unit represented by the formula (3): 
       
         
           
           
               
               
           
         
         wherein 
         a ring A, a ring B, X 3 , Z 1  and Z 2  represent the same meaning as described above; 
         R 1  and R 2  each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, a halogen atom, a silyl group, an amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an alkoxycarbonyl group or a cycloalkoxycarbonyl group, and of these groups, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, a silyl group, an amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an alkoxycarbonyl group and a cycloalkoxycarbonyl group each optionally have a substituent. 
       
     
     
       4. The polymer compound according to  claim 3 , wherein the structural unit represented by the formula (3) is a structural unit represented by the formula (4): 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2 , X 3 , Z 1  and Z 2  represent the same meaning as described above; 
         X 1  and X 2  each independently represent an oxygen atom, a sulfur atom or a selenium atom; and 
         Y 1  represents a nitrogen atom or a group represented by —CR 5 ═, and Y 2  represents a nitrogen atom or a group represented by —CR 6 ═, R 5  and R 6  each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and of these groups, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group each optionally have a substituent. 
       
     
     
       5. The polymer compound according to  claim 4 , wherein X 1 , X 2  and X 3  each represent a sulfur atom. 
     
     
       6. The polymer compound according to  claim 4 , wherein Y 1  and Y 2  represent a group represented by —CH═. 
     
     
       7. The polymer compound according to  claim 1 , wherein Z 1  and Z 2  represent a group represented by formula (Z-1). 
     
     
       8. The polymer compound according to  claim 1 , further comprising a structural unit represented by the formula (5):
     Ar   (5)
 
 wherein 
 Ar represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. 
 
     
     
       9. The polymer compound according to  claim 8 , wherein the polymer compound is an alternate copolymer of the structural unit represented by the formula (1) and the structural unit represented by the formula (5). 
     
     
       10. A compound represented by the formula (6): 
       
         
           
           
               
               
           
         
         wherein 
         a ring A and a ring B each independently represent a heterocyclic ring, and the heterocyclic ring optionally has a substituent other than R 7  and R 8 ; 
         X 3  represents an oxygen atom, a sulfur atom or a selenium atom; 
         Z 1  and Z 2  each independently represent a group represented by the formula (Z-1), a group represented by the formula (Z-2), a group represented by the formula (Z-3), a group represented by the formula (Z-4), a group represented by the formula (Z-5), a group represented by the formula (Z-6) or a group represented by the formula (Z-7); 
         R 1  and R 2  each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, a halogen atom, a silyl group, an amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an alkoxycarbonyl group or a cycloalkoxycarbonyl group, and of these groups, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group, a silyl group, an amino group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkylcarbonyl group, a cycloalkylcarbonyl group, an alkoxycarbonyl group and a cycloalkoxycarbonyl group each optionally have a substituent; R 7  and R 8  each independently represent a hydrogen atom, a halogen atom, a silyl group, a hydroxyl group, a carboxyl group, a borate residue, a boric acid residue or an organotin residue, and of these groups, a silyl group optionally has a substituent; 
       
       
         
           
           
               
               
           
         
         wherein 
         R represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent; and when a plurality of R are present, they may be the same or different. 
       
     
     
       11. The compound according to  claim 10 , wherein the compound represented by the formula (6) is a compound represented by the formula (7): 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2 , R 7 , R 8 , X 3 , Z 1  and Z 2  represent the same meaning as described above; 
         X 1  and X 2  each independently represent an oxygen atom, a sulfur atom or a selenium atom; 
         Y 1  represents a nitrogen atom or a group represented by —CR 5 ═, and Y 2  represents a nitrogen atom or a group represented by —CR 6 ═, R 5  and R 6  each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom, and of these groups, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group and a monovalent heterocyclic group each optionally have a substituent. 
       
     
     
       12. An organic semiconductor composition comprising the polymer compound according to  claim 1 . 
     
     
       13. An organic semiconductor device having a first electrode, a second electrode and an organic semiconductor layer, wherein the organic semiconductor layer contains the polymer compound according to  claim 1 . 
     
     
       14. The organic semiconductor device according to  claim 13 , wherein the device is any of an organic transistor, a photoelectric conversion device, an organic electroluminescent device, an organic field effect type transistor sensor and an organic conductivity modulation type sensor. 
     
     
       15. The organic semiconductor device according to  claim 14 , wherein the device is an organic transistor.